U.S. patent number 3,867,318 [Application Number 05/091,525] was granted by the patent office on 1975-02-18 for photosensitive polymeric esters produced by the condensation of a chloromethyl groups-containing polymer with a carboxyl salt.
This patent grant is currently assigned to Nippon Oil Seal Industry Co., Ltd.. Invention is credited to Yoshinori Imamura, Kiyoshi Maki, Tadatomi Nishikubo, Yoshiko Tomiyama.
United States Patent |
3,867,318 |
Nishikubo , et al. |
February 18, 1975 |
Photosensitive polymeric esters produced by the condensation of a
chloromethyl groups-containing polymer with a carboxyl salt
Abstract
Production of a polymeric ester having photosensitive properties
and the following group in the side chain of its repeating unit
##SPC1## Wherein R is an aliphatic chain, R.sub.1 is hydrogen or a
nitrile group, R.sub.2 is a substituted or non-substituted aromatic
group and a and b are 0 or 1. The ester can be prepared by reacting
polyglycidol or a polyacrylate with an acid halide or by condensing
a polymer with a chloromethyl group in its aliphatic side chain
with a carboxyl salt.
Inventors: |
Nishikubo; Tadatomi (Fujisawa,
JA), Imamura; Yoshinori (Fujisawa, JA),
Tomiyama; Yoshiko (Fujisawa, JA), Maki; Kiyoshi
(Fujisawa, JA) |
Assignee: |
Nippon Oil Seal Industry Co.,
Ltd. (Fujisawa, Kanagawa, JA)
|
Family
ID: |
27290329 |
Appl.
No.: |
05/091,525 |
Filed: |
November 20, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Dec 10, 1969 [JA] |
|
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44-98651 |
Dec 10, 1969 [JA] |
|
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44-98652 |
May 11, 1970 [JA] |
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45-39978 |
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Current U.S.
Class: |
525/404; 522/149;
525/295; 525/298; 525/301; 525/308; 525/359.4; 525/378; 526/193;
526/292.2; 526/292.8; 526/292.9; 526/297; 526/328.5; 430/277.1;
430/287.1; 430/285.1; 525/292; 525/296; 525/303; 525/312; 525/366;
525/408; 526/291; 526/292.6; 526/293; 526/320; 528/366 |
Current CPC
Class: |
C08F
8/00 (20130101); G03F 7/0388 (20130101); C08G
65/329 (20130101) |
Current International
Class: |
C08F
8/00 (20060101); C08G 65/00 (20060101); C08G
65/329 (20060101); G03F 7/038 (20060101); C08g
023/20 () |
Field of
Search: |
;260/89.5H,89.5S,89.1,91.1S,91.1R,2A,2BP
;96/47UA,47UP,2XA,35.1,115,85.7R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Goldstein; Melvin
Assistant Examiner: Pertilla; T.
Attorney, Agent or Firm: Holman & Stern
Claims
What is claimed is: ##SPC8##
1. A method of preparing a polymeric ester comprising condensing a
polymer having a chloromethyl group in the aliphatic side chain of
its repeating unit with a carboxyl salt having the formula:
##SPC9##
wherein M is selected from the group consisting of ammonium and
alkali metals, R.sub.1 is selected from the group consisting of
hydrogen and a nitrile, R.sub.2 is selected from the group
consisting of a substituted and non-substituted aromatic, and a and
b are selected from the group consisting of 0 and 1, the chemical
equivalent of said salt being not less than 0.3 to the chemical
equivalent of the chlorine of said polymer, by adding said salt to
said polymer dissolved in an aprotic polar solvent.
2. A homo- or copolymeric ester capable of film forming and having
the following repeating unit ##SPC10##
wherein R is an alkylene group, R.sub.1 is selected from the group
consisting of hydrogen and a nitrile, R.sub.2 is selected from the
group consisting of a substituted and non-substituted aromatic, and
a and b are
3. A homo- or copolymeric ester capable of film forming and having
the following repeating unit ##SPC11##
wherein R is an alkylene group, R.sub.1 is selected from the group
consisting of hydrogen and a nitrile, R.sub.2 is selected from the
group consisting of a substituted and non-substituted aromatic, and
a and b are
4. A process for the preparation of light-sensitive polymer which
consists essentially of reacting a polymer of epichlorohydrin
containing the recurring unit of the formula, ##SPC12##
with an alkali metal salt of cinnamic acid in the presence of an
aprotic polar solvent to cause substitution of the chlorine atoms
in the chloromethyl groups in the polymer with cinnamate groups,
the chemical equivalent of said salt being not less than 0.3 to the
chemical equivalent of the chlorine of said polymer.
Description
This invention relates to the production of polymeric esters and
relates more particularly to the production of polymeric esters
which exhibit photosensitivity. Such photosensitive polymeric
esters can be prepared by (1) esterifying polyglycidol with an acid
halide, (2) esterifying a polyacrylate with an acid halide, and (3)
condensing a polymer having a chloromethyl group in its aliphatic
side chain with a carboxy salt.
Generically, the photosensitive polymeric ester of this invention
is a polymeric ester having in the side chain of its repeating unit
the following group: ##SPC2##
Wherein R is an aliphatic chain, R.sub.1 is hydrogen, or a nitrile
group, R.sub.2 is a substituted or a non-substituted aromatic
group, and a and b are 0 or 1.
Glycidol (2,3-epoxypropanol) is easily polymerized by boiling in
pyridine, the addition of boron trifluoride diethylether complexes,
etc. to give the polyglycidol of a relatively low molecular weight
polymer. When the polyglycidol is reacted with an acid halide
represented by the following general formula: ##SPC3##
Wherein R.sub.1 is hydrogen or a nitrile group, R.sub.2 is a
substituted or non-substituted aromatic group, X is halogen, and a
and b are 0 or 1, it had been foudn that most of the resultant
novel polyglycidyl esters, except in the case of an ester of
benzoic acid (a=0, b=0), etc, have photosensitivity. However, with
all of the embodiments of this invention, even where a=b=0,
photosensitivity will be found when one of the following groups are
in the side chain: ##SPC4##
Wherein R is an aliphatic chain.
Accordingly, according to one feature of this invention, a novel
polyglycidyl ester can be prepared by reacting a polyglycidol with
an acid halide represented by the above mentioned general formula,
wherein R.sub.2 is an aromatic group such as phenyl, m-nitrophenyl,
p-chlorophenyl, acetoxy phenyl, styryl phenyl, p-methoxyphenyl,
1-naphthyl, 2-naphthyl, 9-anthoryl, 2-furfuryl and 2-thienyl and
the aromatic group may be substituted by substituent groups such as
nitro, chloro, alcohoxy, azide and sulfonazide groups. Examples of
the compounds to be used as an acid halide are benzoyl chloride,
cinnamoyl, chloride, m-nitrocinnamoyl chloride, p-chlorocinnamoyl
chloride, p-methoxycinnamoyl chloride, p-azidobenzoyl chloride,
p-sulfonazido benzoyl chloride, .alpha.-cyanocinnamoyl chloride,
cinnamilideneacetyl chloride, .alpha.-cyanocinnamilideneacetyl
chloride, .beta.-(1)-naphthylacryloyl chloride,
.beta.-(2)naphthylacryloyl chloride, .beta.-(9)-anthorylacryloyl
chloride, .beta.-(2)-furfurylacryloyl chloride,
.alpha.-cyano-.beta.-(2)-furfurylacryloyl chloride,
.beta.-(2)-thienylacryloyl chloride, etc.
The esterification according to this invention may be performed in
a heterogeneous or a homogeneous system. A polyglycidol is soluble
in water but insoluble in general organic solvents such as benzene
and dichloroethane. It is also soluble in aprotic polar solvents
such as dimethylformamide, dimethylsulfoxide,
hexamethylphosphoroamide and N-methylpyrrolidone. The reaction in a
homogeneous system may be carried out in an aprotic polar solvent
and the reaction in a heterogeneous system may be conducted by
Schotten-Baumann reaction. The reaction is performed, under the
usual temperature condition of this kind of reaction, by using a
slight excess of acid halide to the hydroxide group of the
polyglycidol in case of a complete esterification of polyglycidol,
and by using less acid halide than the chemical equivalent of the
hydroxide group in case of the maintenance of the water-solubility
of the resultant ester. Generally, esters are made insoluble in
water by the use of about 0.8 to 1.5 chemical equivalents of acid
halide to the hydroxide group, and still soluble in water by the
use of about 0.5 chemical equivalents of acid halide.
The properties of the resultant polyglycidyl ester varies with its
kind, its esterification value, etc. but generally it is soluble in
acetone, methylethylketone, dimethylformamide, dimethylsulfoxide,
hexamethylphosphoroamide, tetrahydrofuran, etc. and insoluble in
alcohols and aliphatic hydrocarbons such as n-hexane.
These novel esters have film forming capacity and many of them are
photosensitive resins, so that they may be used as photosensitive
films. Moreover, esters which are soluble in organic solvents may
also be used as photosensitive varnishes, paints, etc.
When used as photosensitive resin, the ester of polyvinyl alcohol
cinnamic acid, known as a photosensitive resin has a softening
point of not less than 100.degree.C., is very brittle and soluble
in solvents such as methylethylketone and cyclohexane but its
solubility in acetone, which is an important solvent, is low. In
contrast polyglycidyl ester obtained by this invention is
advantageously employed because of its flexibility in the form of
films and its acetone-solubility.
This embodiment of the instant invention will now be described in
detail by reference to the following illustrative examples:
EXAMPLE 1
0.5 ml. of boron-trifluoride diethylether dissolved in 10 ml. of
dichloroethane were added to 54 g. of glycidol dissolved in 200 ml.
of dichloroethane at 17.degree.C. An exothermic polymerization then
occurred rapidly and the resultant polyglycidol was precipitated.
The catalyst was killed by dissolving the polymer in 50 ml. of weak
ammoniacal water. After drying the polymer out of which the water
was distilled under a reduced pressure, 52 g. of polyglycidol
([.eta.]=0.068) were obtained.
Polyglycidols are soluble in water, dimethylformamide,
hexamethylphosphoroamide, etc. and used for esterification by being
dissolved in these solvents.
10 ml. of an aqueous solution of 1.1 g. of the thus obtained
polyglycidol (15 millimole of glycidol), 5 ml. (concentration; 4
mol/l.) of an aqueous solution of sodium hydroxide and 10 ml. of
methylethylketone were put into a flask, and 2.5 g. (18 millimole)
of benzoyl chloride dissolved in 10 ml. of toluene were added to
the mixture with a vigorous stirring and cooling. After the
reaction proceeded for 2 hours at -4 to 0.degree.C., the organic
phase was separated from the product, washed and added to 300 ml.
of methanol for the reprecipitation of the polymer. 3.4 g. of
polyglycidyl ester of benzoic acid were then obtained.
______________________________________ Elementary analysis values
of this product for (C.sub.10 H.sub.10 C).sub.n Calc. C 67.42% ; H
5.62% Found C 65.39% ; H 5.68%
______________________________________
EXAMPLE 2
50. ml. of an aqueous solution of 5.5 g. (74 millimole) of the same
polyglycidol as in Example 1, 50 ml. (4 mole/l.) of an aqueous
solution of sodium hydroxide and 50 ml. of toluene were put into a
flask, and 15 g. (90 millimole) of cinnamoyl chloride dissolved in
50 ml. of toluene were added to the mixture with a vigorous
stirring and cooling. After 1 hour of the reaction at -4 to
0.degree.C., the organic phase was separated from the product,
washed and added to 500 ml. of n-hexane for the reprecipitation of
the polymer. 15.9 g. of polyglycidyl ester of cinnamic acid were
then obtained.
______________________________________ Elementary analysis values
of this product for (C.sub.12 H.sub.12 O.sub.3).sub.n Calc. C
70.59% ; H 5.88% Found. C 69.87% ; H 5.93%
______________________________________
EXAMPLE 3
7.0 g. (42 millimole) of cinnamoyl chloride were added to 2.7 g.
(36 millimole) of the same polyglycidol as in Example 1 dissolved
in 10 ml. of hexamethyl phosphoroamide and the mixture was reacted
for 5 hours. After the reaction, the polymer was precipitated, when
the product was added to 1 l. of water. 3.8 g. of polyglycidyl
ester of cinnamic acid were then obtained.
EXAMPLE 4
20 ml. of an aqueous solution of 2.2 g. (30 millimole) of the same
polyglycidol as in Example 1, 20 ml. (2 mole/l.) of an aqueous
solution of sodium hydroxide and 20 ml. of methylethylketone were
put into a flask, and 7.6 g. (36 millimole) of m-nitrocinnamoyl
chloride dissolved in 20 ml. of toluene were added to the mixture
with vigorous stirring and cooling. After the reaction proceeded
for 2 hour at -4 to 0.degree.C., the organic phase was separated
from the product, washed and added to 750 ml. of methanol for the
reprecipitation of the polymer. 5.8 g. of polyglycidyl ester of
m-nitrocinnamic acid were then obtained.
______________________________________ Elementary analysis values
of this product for (C.sub.14 H.sub.13 O.sub.5 N).sub.n Calc. C
57.83% ; H 4.42% ; N 5.62% Found. C 58.33% ; H 4.28% ; N 5.73%
______________________________________
EXAMPLE 5
8.4 g. (44 millimole) of .alpha.-cyanocinnamoyl chloride dissolved
in 25 ml. of hexamethylphosphoramide were added to 2.7 g. (36
millimole) of the same polyglycidol as in Example 1 dissolved in 50
ml. of hexamethylphosphoroamide with vigorous stirring and cooling,
and the mixture was reacted for 5 hours. After the reaction, the
polymer was precipitated, when the product was added to 2 L. of
water. This precipitate was then dissolved in 100 ml. of acetone
and again added to 1 l. of water for the reprecipitation of the
polymer. 2.1 g. of polyglycidyl ester of .alpha.-cyanocinnamic acid
were obtained.
______________________________________ Elementary analysis values
of this product for (C.sub.13 H.sub.11 O.sub.3 N).sub.n Calc. C
68.12% ; H 4.80% ; N 6.11% Found. C 65.54% ; H 5.03% ; N 5.98%
______________________________________
EXAMPLE 6
20 ml. of an aqueous solution of 2.2 g. (30 millimole) of the same
polyglycidol as in Example 1, 20 ml. (4 mole/l.) of an aqueous
solution of sodium hydroxide and 20 ml. of methylethylketone were
put into a flask, and 6.9 g. (36 millimole) of cinnamilidenacetyl
chloride were added to the mixture with vigorous stirring and
cooling. After the reaction proceeded for 2 hours at -4 to
1.degree.C., the organic phase was separated from the product,
washed and added to 750 ml. of methanol for the reprecipitation of
the polymer. 3.8 g. of polyglycidyl ester of cinnamilidenacetic
acid were then obtained.
______________________________________ Elementary analysis values
of this product for (C.sub.14 H.sub.14 O.sub.3).sub.n Calc. C
73.04% ; H 6.09% Found. C 72.11% ; H 6.14%
______________________________________
EXAMPLE 7
16 ml. of an aqueous solution of 1.8 g. (24 millimole) of the same
polyglycidol as in Example 1, 15 ml. (4mole/l.) of an aqueous
solution of sodium hydroxide and 10 ml of methylethylketone were
put into a flask, and 6.2 g. (29 millimole) of
.beta.-(1)-naphthylacryloyl chloride were added to the mixture with
vigorous stirring and cooling. After the reaction proceeded for 1.5
hours at -4 to 0.degree.C., the organic phase was separated from
the product, washed and added into 500 ml. of methanol for the
reprecipitation of the polymer. 2.7 g. of polyglycidyl ester of
.beta.-(1)-naphthylacrylic acid were obtained.
______________________________________ Elementary analysis values
of this product for (C.sub.16 H.sub.14 O.sub.3).sub.n Calc. C
75.59% ; H 5.51% Found. C 77.78% ; H 5.63%
______________________________________
EXAMPLE 8
50 ml. of an aqueous solution of 5.55 g. (74 millimole) of the same
polyglycidol as in Example 1, 50 ml. (4mole/l.) of an aqueous
solution of sodium hydroxide and 50 ml. of methylethylketone were
put into a flask, and 18.9 g. (89 millimole) of 2-furfurylacryloyl
chloride dissolved in 50 ml. of toluene were added to the mixture
with vigorous stirring and cooling. After the reaction proceeded
for 1 hour at -3 to 2.degree.C., the organic phase was separated
from the product, washed and added to 1 l. of methanol for the
reprecipitation of the polymer. 8.7 g. of polyglycidyl ester of
2-furfurylacrylic acid were then obtained.
______________________________________ Elementary analysis values
of this product for (C.sub.10 H.sub.10 O.sub.4).sub.n Calc. C
61.84% ; H 5.16% Found. C 60.52% ; H 5.38%
______________________________________
EXAMPLE 9
10 ml. of an aqueous solution of 1.1 g. (15 millimole) of the same
polyglycidol as in Example 1, 10 ml. (4 mole/l.) of an aqueous
solution of sodium hydroxide and 10 ml. of methylethylketone were
put into a flask, and 3.1 g. (18 millimole) of 2-thienylacryloyl
chloride dissolved in 10 ml. of toluene were added to the mixture
with vigorous stirring and cooling. After the reaction proceeded
for 2 hours at -2 to 3.degree.C., the organic phase was separated
from the product, washed and added into 300 ml. of methanol for the
reprecipitation of the polymer. 1.8 g. of polyglycidyl ester of
2-thienylacrylic acid were then obtained.
______________________________________ Elementary analysis values
of this product for (C.sub.10 H.sub.10 O.sub.3 S).sub.n Calc. C
57.14% ; H 4.76% ; S 15.24% Found. C 55.58% ; H 4.82% ; S 14.96%
______________________________________
The above clearly illustrates the production of a novel
polyglycidyl ester according to this invention.
According to a further feature hereof similar concepts may be used
to produce a polymeric ester with photosensitive properties by
reacting a polyacrylate having the following general formula:
##SPC5##
wherein R.sub.1 is hydrogen, a low molecular weight alkyl group, a
nitrile group or halogen and R.sub.2 is an aliphatic radical having
a hydroxyl group, with an acid halide having the following general
formula: ##SPC6##
wherein R.sub.3 is hydrogen or a nitrile group, R.sub.4 is an
aromatic group, X is a halogen and a and b are 0 or 1.
Examples of R.sub.1 of the unit of the polyacrylate are hydrogen,
methyl, ethyl, nitrile groups, chlorine, etc. and those of R.sub.2
are 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,
2,3-dihydroxypropyl, 2-(.beta.-hydroxyethoxy)-ethyl groups, etc.
Exemplary polyacrylates are homopolymers of acrylates such as
2-hydroxyethylacrylate, 2-hydroxypropylacrylate,
3-hydroxypropylacrylate, 2-hydroxyethylmethacrylate,
2-hydroxypropylmethacrylate, 3-hydroxypropylmethacrylate,
2-hydroxyethyl-.alpha.-chloroacrylate,
2-hydroxyethyl-.alpha.-cyanoacrylate,
2-hydroxypropyl-.alpha.-chloroacrylate,
diethyleneglycolmonoacrylate, diethyleneglycolmonomethacrylate and
2,3-dihydroxypropylacrylate, copolymers of these acrylates with
other vinyl compounds such as acrylic acid, alkylacrylate,
methylmethacrylate, acrylonitrile, acrylamide, vinylchloride,
vinlidenechloride, vinyl acetate, styrene, .alpha.-methylstyrene,
p-methoxystyrene, isobutylvinyl ether, 2-chloroethylvinyl ether,
phenylvinyl ether and arylglycidylether, or copolymers of these
acrylates with diolefin compounds such as butadiene, isoprene and
chloroprene.
R.sub.4 is exemplified by the groups set forth hereinabove with
respect to R.sub.2 of formula (2).
In a reaction of a polyacrylate with an acid halide, a slightly
excess of acid halide to the hydroxyl group of the polyacrylate is
generally used, that is to say, in an acid halide to hydroxyl group
chemical equivalent ratio of from about 1.1 to 1.3. The
esterification of the hydroxyl group is carried out almost
completely under such a condition. The partial esterification of of
the hydroxyl group may also be conducted and in this case acid
halide of less chemical equivalent may be used.
The esterification may be performed in a homogeneous or a
hetrogeneous system. Homopolymers and copolymers of acrylate having
a hydroxyl group are insoluble in general organic solvents but
soluble in aprotic polar solvents such as dimethylformamide,
diethylformamide, diethylacetoamide, dimethylsulfoxide,
hexamethylphosphoroamide and N-methylpyrrolidone. A reaction in the
homogeneous system may be conducted by dissolving a polyacrylate
and an acid halide in one of these aprotic polar solvents. Or an
acid halide may directly be added to the polyacrylate dissolved in
the solvent or a tertiary amine, such as pyridine, may also be used
as a dehydrogenhalide agent. Reactions in the heterogeneous system
are, for example, one in which a polyacrylate is added to pyridine
etc. for swelling, followed by the addition of an acid halide for
the reaction therewith or a Schotten Baumann reaction in which an
acid halide dissolved in a solvent immissible with water such as
toluene, methylethylketone, monochlorobenzene and cyclohexanone is
added to an aqueous solution of a polyacrylate in the presence of a
basic substance. For the Schotten Baumann reaction an aqueous
solution of the polymer obtained by the polymerization of the
acrylate may also be employed without a special treatment
thereof.
The properties of this novel polymeric ester vary with the kind of
a newly substituted ester group, but generally it is soluble in
solvents such as acetone, methylethylketone, dimethylformamide,
hexamethylphosphoroamide and tetrahydrofuran, and insoluble in
solvents such as alcohols and hydrocarbons. Also, the obtained
polymeric ester has film-forming capacity. For example, when an
acetone solution of a cinnamic acid ester of
poly-2-hydroxyethylacrylate is flowed on mercury to distil out an
acetone solvent, a flexible strong film is obtained.
It was confirmed that by the observation of the tensile strength of
the obtained film on the copper surface by Erichsen film tester,
there were cracks on the copper sheet at D=8.5 mm., while the film
showed neither cracks nor breaks but showed sufficient resistance
to the applied tensile strength of this value without peeling from
the copper surface.
Further, the obtained ester except non-substituted benzoate (a=b=0)
has photosensitivity and it is useful in photosensitive resins,
varnishes, paints, etc. because it turns insoluble in the presence
of light.
In contrast with the use of the cinnamic acid ester of polyvinyl
alcohol as a photosensitive resin, which, as mentioned above, has a
softening point of not less than 100.degree.C., is very brittle,
and soluble in solvents such as methylethylketone and cyclohexane
but its solubility in acetone, which is an important solvent, is
low, the polymeric ester hereof is advantageously employed because
of its softening point of not more than 100.degree.C., its
flexibility in the form of films and its acetone-solubility. The
photosensitivity of the obtained polymeric ester tends to be higher
in the presence of .alpha.-nitrile, cinnamilidene groups, furan,
thiophene rings, etc. in generally introduced ester groups.
In the case of a photosensitive film obtained from the polymers of
acrylic acid esters of this invention applied on a non-metallic
base such as polyester film, polypropylene film, it shows a very
interesting phenomenon in which the photosensitive film is easily
laminated onto a metallic base such as a copper sheet, an aluminum
sheet and a zinc sheet. That is to say, the photosensitive film
layer on the non-metallic base is easily laminated onto the
metallic base by putting the metallic base on the surface of the
film and pressing the lamination at a temperature of more than the
glass transition temperature. The bond between the photosensitive
film and the metallic base is maintained without the use of an
adhesive, while the bond between the photosensitive film and the
non-metallic base is loose to the extent that the non-metallic base
can easily peel from the film layer by hand but it is maintained
unless the base is intentionally peeled from the layer.
Such photosensitive lamination comprising a metallic base, a
photosensitive film and a non-metallic base has a very important
utility. That is to say, the non-metallic base works as a
protective base when the lamination is used as a photosensitized
plate, further in the case of a shading non-metallic base, the
photosensitization of the lamination during its preservation is
difficult. Therefore, a quality lamination of a stable
photosensitivity can be supplied to customers in the form of a
photosensitized plate. The photosensitive lamination, with or
without the non-metallic protective base, has a good
photosensitivity, although such protective base is preferred to
protect the lamination. Practically, the photosensitive lamination
will be supplied to a customer with the protective base on the
film. The base is peeled off in actual use.
In the use of a lamination with a photosensitive film formed on the
metallic or non-metallic base, a negative is put on the film. Then
this is exposed to a chemical lamp, etc. and after the exposure,
the unexposed areas of the film are dissolved and washed away with
a solvent, such a monochlorobenzene, which dissolve polyacrylate
used for film forming. As a result, the exposed areas leave the
opposite images to those of the negative because the exposed areas
are cross-linked to become insoluble in the solvent. Further, in
the use of a sheet metal as the base, the metallic base can be
etched with an etching agent such as an aqueous solution of ferric
chloride, and the exposed areas are sufficiently resistant to the
etching agent, thus giving clear images.
Further examples of this embodiment of the instant inventive
concepts are as follows:
EXAMPLE A
0.08 g. of azobisisobutylnitrile were added to 75 g. of
2-hydroxyethylacrylate (HEA) dissolved in 150 ml. of
hexamethylphosphoroamide and the mixture was polymerized in N.sub.2
gas for 1 hour at 60.degree.C. and further for 2 hours at
80.degree.C. Poly-2-hydroxyethylacrylate (PHEA) was then obtained.
([.eta.]=0.60)
EXAMPLE B
0.9 g. of potassium persulfate were added to 90 g. of
2-hydroxy-ethylacrylate (HEA) dissolved in 900 ml. of water and the
mixture was polymerized in N.sub.2 gas at 60 .degree. C for 1 hour.
After the reaction the product was added to 3 L. of acetone for the
precipitation of the polymer. 81 g. of poly-2-hydroxyethylacrylate
(PHEA) were then obtained. ([.eta.]=0.93)
EXAMPLE C
0.05 g. of azobisisobutylnitrile were added to 50 g. of
2-hydroxyethylacrylate (HEA) dissolved in 200 ml. of
dimethylformamide and the mixture was polymerized in N.sub.2 gas
for 3 hours at 65.degree.C. and further for 2 hours at 80.degree.C.
Poly-2-hydroxyethylacrylate (PHEA) was then obained.
([.eta.]=0.43)
EXAMPLE D
0.15 g. of azobisisobutylnitrile were added to 150 g. of
2-hydroxypropylacrylate (HPA) dissolved in 150 ml. of
hexamethylphosphoroamide and the mixture was polymerized in N.sub.2
gas for 1 hour at 60.degree.C. and further for 1 hour at
80.degree.C. Poly-2-hydroxypropylacrylate (PHPA) was then obtained.
([.eta.]=0.77)
EXAMPLE E
0.5 g. of azobisisobutylnitrile were added to 50 g. of
2-hydroxypropylmethacrylate dissolved in 180 ml. of
hexamethylphosphoroamide and the mixture was polymerized in N.sub.2
gas for 3 hours at 60.degree.C. Poly-2-hydroxypropylmethacrylate
was then obtained. ([.eta.]=0.43)
EXAMPLE F
0.2 g. of azobisisobutylnitrile were added to 75 g. of
2-hydroxyethylacrylate and 25 g. of n-butylacrylate both dissolved
in 300 ml. of hexamethylphosphoroamide and the mixture was
polymerized in N.sub.2 gas for 3 hours at 60.degree.C. and further
for 2 hours at 80.degree.C. 2-hydroxyethylacrylate-n-butylacrylate
copolymer was then obtained.
EXAMPLE G
0.5 g. of azobisisobutylonitrile were added to 40 g. of
2-hydroxyethylacrylate and 10 g. of n-butylacrylate both dissolved
in 40 ml. of dimethylsulfoxide and the mixture was polymerized in
N.sub.2 gas for 3 hours at 60.degree.C. and further for 2 hours at
80.degree.C. 2-hydroyethylacrylate-n-butylacrylate copolymer was
then obtained.
EXAMPLE H
0.1 g. of azobisisobutylnitrile were added to 75 g. of
2-hydroxyethylacrylate and 75 g. of styrene both dissolved in 150
ml. of hexamethylphosphoroamide and the mixture was polymerized in
N.sub.2 gas for 3 hours at 60.degree.C. and further for 2 hours at
80.degree.C. 2-hydroxyethylacrylate-styrene copolymer was then
obtained. ([.eta.]=0.62)
EXAMPLE 10
12.9 g. of cinnamoyl chloride dissolved in 50 ml. of
hexamethylphosphoroamide were added, with stirring, to 7.5 g. of
PHEA obtained in Example A dissolved in100 ml. of
hexamethylphosphoroamide and the mixture was reacted at
50.degree.C. for 5 hours. After the reaction the product was added
into 1.5 l. of water for the precipitation of the polymer. The
obtained polymer was again dissolved in 200 ml. of acetone and the
solution was added into 1.5 l. of water for reprecipitation. 9.0 g.
of the ester of PHEA-cinnamic acid were then obtained.
It was confirmed from the results of an elementary analysis, I.R.
spectrum and N.M.R. spectrum observations of the obtained polymeric
ester that it was completely esterificated, that is to say, with
neither absorption of a hydroxide group shown in the I.R. spectrum
between 3500-3400 cm..sup.-.sup.1 nor chemical shift of an
alcoholic hydroxide group shown in the N.M.R. spectrum.
______________________________________ Elementary analysis of this
product for (C.sub.14 H.sub.14).sub.4).sub.n Calc. C : 68.29% , H :
5.69% Found. C : 66.98% , H : 5.67%
______________________________________
EXAMPLE 11
1.5 g. of the cinnamate ester of PHEA obtained in Example 10
dissolved in 7.5 ml. of cyclohexanone were applied on the surface
of a sheet glass by a whirling applying device. After drying it, a
film of 1.mu. thickness was obtainted on the glass surface.
A step tablet No. 2 (made by Kodak Company) with 21 stepped images
was put on the produced photosensitive film on the surface of the
sheet glass and it was exposed for a period of 21 minutes to 40
watt chemical lamp at a distance of 10 cm. After the exposure the
unexposed areas of the photosensitive film were dissolved and
washed away with monochlorobenzene. As a result, on the sheet glass
the images were printed, of which those up to the third step were
distinguishable.
EXAMPLE 12
1.5 g. of the cinnamate ester of PHEA obtained in Example 10 and
0.12 g. of 5-nitroacenaphtene as a sensitizer, both dissolved in
7.5 ml. of cyclohexanone, were applied on the surface of a sheet
glass by a whirling applying device. After drying them, a film of
less than 1 .mu. thickness was obtained on the surface of the sheet
glass.
A step tablet No. 2 (made by Kodak Company) with 21 stepped images
was then put on the resultant photosensitive film on the glass
surface and it was exposed for a period of 4 minutes to a 40 watt
chemical lamp at a distance of 10 cm. After the exposure, the
unexposed areas of the photosensitive film were dissolved and
washed away with monochlorobenzene. As a result, on the sheet glass
the images were printed, of which those up to the 17th step were
distinguisable.
The same result was obtained when N-acetyl-4-nitro-1-naphthylamine
or 4,4'-(bisdimethylamino)benzophenone was employed as the
sensitizer in the place of 5-nitroacenaphthene.
EXAMPLE 13
A copper sheet was coated with 3.0 g. of the cinnamate ester of
PHEA obtained in Example 10 and 0.24 g. of 5-nitroacenaphthene,
both dissolved in 15 ml. of cyclohexanone, to give a film thickness
of 100 .mu. by using a knife-coater. After drying thus provided
coating at 50.degree.C. for 1 hour, a film of 12 .mu. thickness was
obtained on the copper surface.
A negative was then put on the obtained photosensitive film on the
copper surface and it was exposed for a period of 4 minutes to a 40
watt chemical lamp at a distance of 10 cm. After the exposure the
unexposed areas of the film were dissolved and washed away with
monochlorobenzene. Then, this film was treated with an aqueous
solution of ferric chloride for etching. The insoluble areas of the
film were sufficiently resistant to the etching solution and clear
images on the copper were obtained
It was confirmed that by the observation of the strength of the
film having 12 .mu. thickness on the copper surface by Erichsen
film tester, there were cracks on the copper sheet at D=8.5 mm.,
while the film did not show cracks but showed sufficient resistance
to the applied stress of this value.
EXAMPLE 14
A polyester film was coated with 3.0 g. of the cinnamate ester of
PHEA obtained in Example 10 and 0.24 g. of 5-nitroacenaphthene as a
sensitizer both dissolved in 15 ml. of cyclohexanone to give a film
thickness of 100 .mu., by using a knife-coater. After drying thus
formed coating at 50.degree.C. for 1 hour, a film of 12 .mu.
thickness was obtained on the polyester film surface.
The photosensitive film layer on the polyester film surface was
well laminated to the surface of a copper sheet using heated
pressure rollers at a temperature of 100.degree.C. and the
polyester film was easily peeled from the photosensitive film
layer.
A polypropylene film used in place of the polyester one also showed
a successful result.
EXAMPLE 15
20 ml. of pyridine were added to 10.0 g. of PHEA obtained in
Example C dissolved in 100 ml. of dimethylformamide. 17.2 g. of
cinnamoyl chloride dissolved in 50 ml. of dimethylformamide were
added with stirring to and reacted with the mixture at 50.degree.C.
for 5 hours. After the reaction the product was added into 2 l. of
methanol for the precipitation of the polymer. 13.5 g. of the ester
of PHEA-cinnamic acid were then obtained.
EXAMPLE 16
50 ml. of methylethylketone and 50 ml. of an aqueous solution of
sodium hydroxide (concentration 2 mole/l.) were added to 3.64 g. of
PHEA obtained in Example B dissolved in 50 ml. of water and the
mixture was cooled to -3.degree.C. 7.0 g. of cinnamoyl chloride
dissolved in 50 ml. of methylethylketone were added, with stirring,
to and reacted with the mixture at -5.degree. to 4.degree.C. for 1
hour. After the reaction the organic phase of the product was added
into 1 l. of methanol for the precipitation of the polymer. 5.8 g.
of the ester of PHEA-cinnamic acid were then obtained.
EXAMPLE 17
11.5 g. of cinnamoyl chloride dissolved in 50 ml. of
hexamethylphosphoroamide were added to 7.5 g. of PHEA obtained in
Example D dissolved in 100 ml. of hexamethylphosphoroamide and the
mixture was reacted at 50.degree.C. for 5 hours. After the reaction
the product was added into 1.5 l. of water for the precipitation of
the polymer. The polymer was dissolved again in 200 ml. of
tetrahydrofuran and the solution was added into 1.5 l. of water for
reprecipitation. 11.3 g. of the ester of PHPA-cinnamic acid were
then obtained.
It was confirmed from the results of an elementary analysis, I.R.
spectrum and N.M.R. spectrum observations of obtained polymeric
ester that it was completely esterificated, that is to say, with
neither absorption of a hydroxide group shown in the I.R. spectrum
between 3500-3400 cm..sup.-.sup.1 nor chemical shift of an
alcoholic hydroxide group shown in the N.M.R. spectrum.
______________________________________ Elementary analysis of this
product for (C.sub.15 H.sub.16 O.sub.4).sub.n Calc. C : 69.23% , H
: 6.15% Found. C : 67.98% , H : 5.99%
______________________________________
EXAMPLE 18
13.9 g. of cinnamoyl chloride dissolved in 50 ml. of
hexamethylphosphoroamide were added to 10.0 g. of
poly-2-hydroxypropylmethacrylate obtained in Example E disolved in
100 ml. of hexamethylphosphoroamide and the mixture was reacted at
60.degree.C. for 4 hours. After the reaction the product was added
into 2 l. of water for the precipitation of the polymer. The
polymer was again disolved in 200 ml. of acetone and the solution
was added into 2 l. of methanol for reprecipitation. 6.0 g. of the
ester of poly-2-hydroxypropylmethacrylate-cinnamic acid were then
obtained.
______________________________________ Elementary analysis of this
product for (C.sub.16 H.sub.18 O.sub.4).sub.n Calc. C : 70.10% , H
: 6.57% Found. C : 68.03% , H : 6.87%
______________________________________
EXAMPLE 19
9.8 g. of m-nitrocinnamoyl chloride dissolved in 30 ml. of
hexamethylphosphoroamide were added to 4.5 g. of PHEA obtained in
Example A dissolved in 30 ml. of hexamethylphosphoroamide and the
mixture was reacted at 50.degree.C. for 5 hours. After the reaction
the product was added into 2 l. of water for the precipitation of
the polymer. The polymer was again dissolved in 300 ml. of acetone
and the solution was added into 2 l. of methanol for
reprecipitation. 6.7 g. of the ester of PHEA-m-nitrocinnamic acid
were then obtained.
______________________________________ Elementary analysis of this
product for (C.sub.14 H.sub.13 O.sub.6).sub.n Calc. C : 57.72% , H
: 4.47% , N : 4.81% Found. C : 56.56% , H : 4.21% , N : 4.79%
______________________________________
EXAMPLE 20
9.7 g. of p-chlorocinnamoyl chloride dissolved in 20 ml. of
hexamethylphosphoroamide were added to 4.64 g. of PHEA obtained in
Example A dissolved in 60 ml. of hexamethylphosphoroamide and the
mixture was reacted at 50.degree.C. for 5 hours. After the reaction
the product was added into 2 l. of methanol for the precipitation
of the polymer. The polymer was again dissolved in 100 ml. of
methylethylketone and the solution was added into 2 l. of methanol
for reprecipitation and purification. 5.7 g. of
PHEA-p-chlorocinnamic acid were then obtained.
______________________________________ Elementary analysis of this
product for (C.sub.14 H.sub.13 O.sub.4 Cl).sub.n Calc. C : 59.89% H
: 4.63% Cl : 12.66% Found. C : 57.96% H : 4.38% Cl : 12.43%
______________________________________
EXAMPLE 21
14.8 g. of .alpha.-cyanocinnamoyl chloride dissolved in 50 ml. of
hexamethylphosphoroamide were added to 7.5 g. of PHEA obtained in
Example A dissolved in 100 ml. of hexamethylphosphoroamide with
stirring and the mixture was reacted at 50.degree.C. for 5 hours.
After the reaction the product was added into 2 l. of water for the
precipitation of the polymer. The polymer was dissolved in 200 ml.
of acetone and the solution was added into 1 l. of methanol for
reprecipitation. 9.0 g. of the ester of PHEA-.alpha.-cyanocinnamic
acid were then obtained.
______________________________________ Elementary analysis of this
product for (C.sub.15 H.sub.13 O.sub.4 N).sub.n Calc. C : 66.42% H
: 4.80% N : 5.17% Found. C : 64.84% H : 4.96% N : 4.99
______________________________________
EXAMPLE 22
13.3 g. of .alpha.-cyanocinnamoyl chloride dissolved in 100 ml. of
hexamethylphosphoroamide were added to 7.5 g. of PHPA obtained in
Example D dissolved in 100 ml. of hexamethylphosphoroamide with
stirring and the mixture was reacted at 50.degree.C. for 5 hours.
After the reaction the product was added into 2 l. of water for the
precipitation of the polymer. The polymer was again dissolved in
200 ml. of acetone and the solution was added into 2 l. of methanol
for the precipitation. 8.2 g. of the ester of
PHPA-.alpha.-cyanocinnamic acid were then obtained.
______________________________________ Elemetary analysis of this
product for (C.sub.16 H.sub.15 O.sub.4 N).sub.n Calc C : 67.37% H :
5.26% N : 4.91% Found. C : 67.56% H : 5.84% N : 4.26%
______________________________________
EXAMPLE 23
9.0 g. of cinnamilidenacetyl chloride dissolved in 30 ml. of
hexamethylphosphoroamide were added to 4.5 g. of PHEA obtained in
Example A dissolved in 60 ml. of hexamethylphosphoroamide with
stirring and the mixture was reacted at 50.degree.C. for 5 hours.
After the reaction the product was added into 2 l. of water for the
precipitation of the polymer. The polymer was again dissolved in
200 ml. of acetone and the solution was added into 2 l. of methanol
for reprecipitation. 5.4 g. of the ester of PHEA-cinnamilidenacetic
acid were then obtained.
______________________________________ Elementary analysis of this
product for (C.sub.16 H.sub.16 O.sub.4).sub.n Calc. C : 70.60% H :
5.88% Found. C : 68.72% H : 5.98%
______________________________________
EXAMPLE 24
3.0 g. of the cinnamilidenacetate ester of PHEA obtained in Example
23 and 0.24 g. of 5-nitroacenaphthene as a sensitizer, both
dissolved in 15 mil. of cyclohexanone, were applied onto the
surface of a sheet glass by a whirling applying device. After
drying them, a film of less than 1 .mu. thickness was obtained on
the surface of the sheet glass.
The exposure was carried out in a similar way to Example 12 for a
period of 2 minutes to a chemical lamp. As a result, on the sheet
glass the images of the step tablet were printed, of which those up
to the third step were distinguishable.
EXAMPLE 25
10.1 g. of .alpha.-cyanocinnamilidenacetyl chloride dissolved in 30
ml. of hexamethylphosphoroamide were added to 4.5 g. of PHEA
obtained in Example A dissolved in 60 ml. of
hexamethylphosphoroamide with stirring and the mixture was reacted
at 50.degree.C. for 5 hours. After the reaction the product was
added into 2 l. of water for the precipitation of the polymer. The
polymer was again dissolved in 200 ml. of acetone and then the
solution was added into 2 l. of methanol for reprecipitation. 9.0
g. of the ester of PHEA-.alpha.-cyanocinnamilidenacetic acid were
then obtained.
______________________________________ Elementary analysis of this
product for (C.sub.17 H.sub.15 O.sub.4 N).sub.n Calc. C : 68.69% H
: 5.05% N : 4.71% Found. C : 67.43% H : 5.73% N : 4.25%
______________________________________
EXAMPLE 26
10.7 g. of .beta.-(1)-naphthylacryloyl chloride dissolved in 30 ml.
of hexamethylphosphoroamide were added to 4.5 g. of PHEA obtained
in Example A dissolved in 60 ml. of hexamethylphosphoroamide with
stirring and the mixture was reacted at 50.degree.C. for 5 hours.
After the reaction, the product was added into 2 l. of water for
the precipitation of the polymer. The polymer was again dissolved
in 200 ml. of acetone and the solution was added into 2 l. of
methanol for reprecipitation. 7.1 g. of the ester of
PHEA-.beta.-(1)-naphthylacrylic acid were then obtained.
______________________________________ Elementary analysis of this
product for (C.sub.16 H.sub.14 O.sub.4).sub.n Calc. C : 71.19% H :
5.19% Found. C : 69.98% H : 5.41%
______________________________________
EXAMPLE 27
11.1 g. of .beta.-(2)-furfurylacryloyl chloride dissolved in 50 ml.
of hexamethylphosphoroamide were added to 7.5 g. of PHEA obtained
in Example A dissolved in 100 ml. of hexamethylphosphoroamide with
stirring and the mixture was reacted at 50.degree.C. for 5 hours.
After the reaction the product was added into 2 l. of water for the
precipitation of the polymer. The polymer was again dissolved in
300 ml. of acetone and the solution was added into 2 l. of methanol
for reprecipitation. 5.8 g. of the ester of
PHEA-.beta.-(2)-furfurylacrylic acid were then obtained.
______________________________________ Elementary analysis of this
product for (C.sub.12 H.sub.12 O.sub.5).sub.n Calc. C : 61.01% H :
5.09% Found. C : 61.15% H : 4.83%
______________________________________
EXAMPLE 28
14.0 g. of .alpha.-cyano-.beta.-(2)-furfurylacryloyl chloride
dissolved in 50 ml. of hexamethylphosphoroamide were added to 7.5
g. of PHEA obtained in Example A dissolved in 100 ml. of
hexamethylphosphoroamide with stirring and the mixture was reacted
at 50.degree.C. for 5 hours. After the reaction the product was
added into 2 l. of n-hexane for the precipitation of the polymer.
The polymer was again dissolved in 100 ml. of acetone and the
solution was added into 5 l. of water for reprecipitation. 9.1 g.
of the ester of PHEA-.alpha.-cyano-.beta.-(2)-furfurylacrylic acid
were then obtained.
______________________________________ Elementary analysis of this
product for (C.sub.13 H.sub.11 O.sub.5 N).sub.n Calc. C : 59.79% H
: 4.22% N : 5.36% Found. C : 58.67% H : 4.54% N : 5.11%
______________________________________
EXAMPLE 29
8.6 g. of 2-thienylacryloyl chloride dissolved in 30 ml. of
hexamethylphosphoroamide were added to 4.6 g. of PHEA obtained in
Example A dissolved in 60 ml. of hexamethylphosphoroamide with
stirring and the mixture was reacted at 50.degree.C. for 5 hours.
After the reaction the product was added into 1.7 l. of methanol
for the precipitation of the polymer. 5.7 g. of the ester of
PHEA-2-thienylacrylic acid were obtained.
______________________________________ Elementary analysis of this
product for (C.sub.12 H.sub.13 O.sub.4 S).sub.n Calc. C : 57.14% H
: 4.76% S : 12.70% Found. C : 57.03% H : 4.52% S : 12.54%
______________________________________
EXAMPLE 30
1.48 g. of cinnamoyl chloride dissolved in 20 ml. of
hexamethylphosphoroamide were added to 10.0 g. of
2-hydroxyethylacrylate-n-butylacrylate copolymer obtained in
Example F dissolved in 50 ml. of hexamethylophosphoroamide with
stirring and the mixtire was reacted at 55.degree.C. for 5 hours.
After the reaction the product was added into 2 l. l. water for the
precipitation of the polymer. The polymer was again dissolved in
100 ml. of acetone and the solution was added into 1.5 l. of
methanol for reprecipitation, 9.5 g. of the copolymer of
n-butylacrylate-2-hydroxyethylacrylate ester of cinnamic acid were
then obtained.
EXAMPLE 31
5 ml. of pyridine were added to 5.0 g. of
2-hydroxyethylacrylate-n-butylacrylate copolymer obtained in
Example G dissolved in 50 ml. of dimethylsulfoxide and 6.9 g. of
cinnamoyl chloride dissolved in 20 ml. of chloroform were added
with stirring to and reacted with the mixture of 30.degree.C. for 5
hours. After the reaction the product was added into 1 l. of water
for precipitation of the polymer. 5.8 g. of the copolymer of
n-butylacrylate-2-hydroxyethylacrylate ester of cinnamic acid were
then obtained.
EXAMPLE 32
14.8 g. of cinnamoyl chloride dissolved in 50 ml. of
hexamethylphosphoroamide were added to 15.0 g. of
2-hydroxyethylacrylate-styrene copolymer obtained in Example H
dissolved in 100 ml. of hexamethylphosphoroamide and the mixture
was reacted at 50.degree.C. for 5 hours. After the reaction the
product was added into 2 l. of water for the precipitation of the
polymer. The polymer was again dissolved in 200 ml. of acetone and
the solution was added into 2 l. of methanol for reprecipitation.
40 g. of the copolymer of styrene-2-hydroxyethylacrylate ester of
cinnamic acid were then obtained.
EXAMPLE 33
7.1 g. of benzoyl chloride dissolved in 30 ml. of
hexamethylphosphoroamide were added to 4.64 g. of PHEA obtained in
Example A dissolved in 60 ml. of hexamethylphosphoroamide and the
mixture was reacted for 5 hours with keeping a reaction temperature
at 50.degree.C. After the reaction the product was added into 2 l.
of water for the precipitation of the polymer. The polymer was
again dissolved in 100 ml. of methylethylketone and the solution
was added into 2 l. of water for reprecipitation. 3.6 g. of the
ester of PHEA-benzoic acid were then obtained.
______________________________________ Elementary analysis of this
product for (C.sub.12 H.sub.12 O.sub.4).sub.n Calc. C : 65.45% H :
5.45% Found. C : 63.32% H : 5.55%
______________________________________
EXAMPLE 34
9.5 g. of p-azidobenzoyl chloride dissolved in 50 ml. of
hexamethylphosphoroamide were added to 5.8 g. of PHEA obtained in
Example A dissolved in 50 ml. of hexamethylphosphoroamide and the
mixture was reacted with keeping a temperature at 30.degree.C. for
5 hours. After the reaction, the product was added to 500 ml. of
methanol for the precipitation of the polymer. The polymer was
again dissolved in 50 ml. of methylethylketone and the solution was
added into 500 ml. of methanol for reprecipitation. 9.4 g. of the
ester of PHEA-p-azidobenzoic acid, were then obtained.
Since the measurement of the I.R. and N.M.R. spectrums of the
obtained polymer did not show the presence of an alcoholic
hydroxide group, the esterification of the polymer believed to have
progressed completely.
______________________________________ Elementary analysis of this
product for (C.sub.12 H.sub.11 O.sub.4 N.sub.3).sub.n Calc. N :
16.09% Found. N : 15.99% ______________________________________
EXAMPLE 35
4.0 g. of p-azidobenzoyl chloride dissolved in 15 ml. of
dimethylformamide were added to 2.3 g. of PHEA obtained in Example
A dissolved in 40 ml. of dimethylformamide and the mixture was
reacted with keeping a temperature at room temperature for 5 hours.
After the reaction, the product was added into 300 ml. of methanol
for the precipitation of the polymer. The polymer was again
dissolved in 20 ml. of methylethylketone and the solution was added
into 300 ml. of methanol for reprecipitation. 1.1 g. of the ester
of PHEA-p-azidobenzoic acid were then obtained.
EXAMPLE 36
4.0 g. of p-azidobenzoyl chloride dissolved in 15 ml. of
hexamethylphosphoroamide were added to 2.9 g. of
poly-2-hydroxypropylmethacrylate obtained in Example E dissolved in
50 ml. of hexamethylphosphoroamide and the mixture was reacted with
keeping a temperature at 0.degree.C. for 5 hours. After the
reaction, the product was treated as in Example 35 and 3.5 g. of
the ester of poly-2 -hydroxypropylmethacrylate-p-azidobenzoic acid
were then obtained.
______________________________________ Elementary analysis of the
product for (C.sub.14 H.sub.15 O.sub.4 N.sub.3).sub.n Calc. N :
14.53% Found. N : 14.45% ______________________________________
EXAMPLE 37
4.0 g. of p-azidobenzoyl chloride dissolved in 15 ml. of
hexamethylphosphoroamide were added to 3.6 g. of
2-hydroxyethylacrylate-n-butylacrylate copolymer obtained in
Example F dissolved in 25 ml. of hexamethylphosphoroamide and the
mixture was reacted with keeping a temperature at 50.degree.C. for
2 hours. After the reaction, the product was treated as in Example
35 and 2.0 g. of the copolymer of
2-hydroxyethylacrylate-n-butylacrylate ester of p-azidobenzoic acid
were then obtained.
In each of the above mentioned Examples, the proportion of acid
chloride to the hydroxide group contained in the polyacrylate was
such that the former was in slight excess. That is to say, the
chemical equivalent of the acid halide to that of a hydroxide group
is 1.04 in Example 34, 1.10 in Examples 27,35,36 and 37, 1.25 in
Examples 29 and 33, 1.30 in Example 16 and in the other
Examples.
EXAMPLE 38 0.023 g. of azobisisobutylonitrile were added to 21.0 of
2-hydroxyethyl acrylate and 1.7 g. of vinyl acetate both dissolved
in 25 ml. of hexamethylphosphoroamide and the mixture was reacted
at 60.degree.C. for 4 hours. The copolymer of
2-hydroxyethylacrylate-vinylacetate was obtained.
([.eta.]=1.35)
After 75 ml. of hexamethylphosphoroamide were added to the reacted
solution the mixture was reacted at 50.degree.C. for 5 hours. The
reacted solution was added into 3 l. of methanol for the
precipitation of a polymer. The polymer was again dissolved in 150
ml. of methylethylketone for a reprecipitation. 25.8 g. of
cinnamate ester of the copolymer of
2-hydroxyethylacrylate-vinylacetate were then obtained. (T.sub.g =
65.degree.C)
EXAMPLE 39
The cinnamate ester of the copolymer of
2-hydroxyethyl-acrylate-vinylacetate obtained in Example 38 are
treated in a similar way to Example 12. As a result, on the sheet
glass the images of the step tablet were printed, of which those up
to the 16th step were distinguishable.
The above Examples serve to illustrate the second embodiment of
this invention.
As indicated previously, this invention also relates to the
production of a polymeric ester by condensing a polymer having a
chloromethyl group in its aliphatic side chain with a carboxyl
salt.
In activity, the chlorine of the chloromethyl group of polymers
having the same group in their aliphatic side chain such as
homopolymers or copolymers of epichlorohydrin, vinylchloracetate,
2-chloroethylvinyl ether, 2-chloroethylacrylate and
3,3-bis-(chloromethyl)-oxtane is less than the bromine of
bromomethyl groups and also than the chlorine of the chloromethyl
group of p-chloromethylstyrene polymers, which, in contast, has a
high activity. For that reason chlorine in the chloromethyl group
of polymers having the same group in their aliphatic side chain is
generally nearly chemically inert, leading to a rare situation in
which the chlorine of chloromethyl groups is employed as a
functional group in reaction with such materials.
It has now been found that the condensation reaction of a polymer
having in its aliphatic side chain a chloromethyl group containing
such inert chlorine with a carboxyl salt having the following
general formula: ##SPC7##
wherein R.sub.1 represents hydrogen or a nitrile group, R.sub.2 is
an aromatic group, M is an ammonium group or an alkali metal, and a
and b are 0 or 1 in an aprotic polar solvent proceeds very smoothly
to prepare polymeric esters most of which have
photosensitivity.
Examples of R.sub.2 of a carboxyl salt such as represented by
formula (8) are substituted or non-substituted aromatic groups such
as phenyl, nitrophenyl, chlorophenyl, hydroxyphenyl, acetoxyphenyl
or styrlylphenyl, with the substituted groups of the above phenyl
rings being positioned in ortho, meta or para, 1-naphtyl,
2-naphthyl, 9-anthoryl, 2-furfuryl, 2-thienyl, 4-pyridil,
p-azidophenyl, and p-sulfonazidophenyl groups. Examples of
carboxylic acid forming ammonium salts or alkali metal salts used
in this invention are benzoic acid, p-nitrobenzoic acid,
p-azidobenzoic acid, cinnamic acid, m-nitrocinnamic acid,
p-chlorocinnamic acid, p-methoxycinnamic acid,
.alpha.-cyanocinnamic acid, cinnamilidenacetic acid,
.alpha.-cyanocinnamilidenacetic acid, .beta.-(1) -naphthylacrylic
acid, .beta.-(2 )-naphthylacrylic acid, .beta.-(9)-anthorylacrylic
acid, .beta.-(2)-furfurylacrylic acid,
.alpha.-cyano-.beta.-(2)-furfurylacrylic acid,
.beta.-(2)-thienylacrylic acid, .beta.-(4)-pyridylacrylic acid and
p-sulfonazidobenzoic acid, and these acids are employed in the
condensation reaction in the form of ammonium, sodium, potassium
salts, etc.
A chloromethyl group in the side chain of a polymer which is
condensed with a carboxyl salt is generally monochloromethyl group,
but hydrogen left in the methyl group may also be substituted by a
halogen atom, an alkyl group, a hydroxyalkyl group, etc.
A condensation reaction of a polymer having the chloromethyl group
in the aliphatic side chain with a carboxyl salt is performed by
adding the carboxyl salt to the polymer dissolved in aprotic polar
solvents such as hexamethyl-phosphoroamide, dimethylformamide,
diethylformamide, dimethylacetoamide, dimethylsulfoxide and
N-methylpyrrolidone. The condensation reaction proceeds smoothly
without a catalyst depending on the type of the solvent, but
generally proceeds at a high yield and a high esterification degree
by the addition of a quaternary ammonium salt such as
methyl-triethylammonium iodide. In contrast, when a generally used
inert organic solvent except aprotic polar ones is employed, an
esterification reaction does not proceed at all, even if the
solvent dissolves the polymer having a chloromethyl group.
In a reaction, a slight excess of carboxyl salt to the chemical
equivalent of the chlorine of the polymer is generally employed but
a polymeric ester usable for a photosensitive resin, is also
obtained at a chemical equivalent of not less than 0.3. The
obtained polymeric ester is soluble in generally used solvents such
as acetone, benzene, toluene, chloroform, dimethylformamide,
tetrahydrofuran and hexamethylphosphoroamide.
Again, as mentioned previously, when used as a photosensitive resin
the ester of polyvinylalcohol-cinnamic acid, a known photosensitive
resin, has a low film-forming capacity, is very brittle in the form
of films, is soluble in solvents such as methylethylketone and
cyclohexane and its solubility in acetone, which is an important
solvent, is low. In contrast polymeric ester obtained by this
embodiment of the instant inventive concepts is advantageously
employed for its film-forming capacity, its flexibility in the form
of films and its acetone-solubility.
In a method of preparing polymeric ester by this invention, when
the chemical equivalent of carboxyl salt is less than that of
chlorine in the chloromethyl group of the polymer to be esterified,
an ester of a low esterification degree is obtained. It forms a
kind of copolymer, so that a polymeric ester having necessary
physical properties may be obtained by controlling the
esterification degree.
Further Examples illustrating this embodiment are as follows:
EXAMPLES 40-58
A carboxyl salt and, if necessary, methyltriethyl-ammonium iodide
as a catalyst were added to a polymer having a chloromethyl group
in the aliphatic side chain dissolved in an aprotic polar solvent
and the mixture was reacted at a given temperature for given hours.
After the reaction the reacted mixture was added into water for the
precipitation of the product. The precipitate was dissolved in
methylethylketone and the solution was again added into water for
reprecipitation and purification.
The obtained polymeric ester was confirmed by I.R. spectrum and
N.M.R. spectrum observations, and its esterification degree was
observed by the quantitiative analysis of the unreacted chlorine
remaining in the product and included in each monomer unit by the
method of microanalyais of halogen.
The results of the analysis are shown in the following table:
TABLE
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Polymer Carboxyl Salt Solvent Cata- Reaction Product lyst condition
Ex. abbre- g. mole Compound g. mole abbre- ml. g. .degree.C. hrs.
g. esteri- via- via- fication tion tion degree
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40 PCEA 6.73 0.05 potassium cinnamate 9.3 0.05 HMPA 70 1.0 100 10
11.0 0.98 41 PCEA 6.73 0.05 ammonium cinnamate 10.1 0.05 HMPA 70
1.0 100 10 10.5 0.93 42 PECH 4.63 0.05 potassium cinnamate 11.2
0.06 HMPA 40 1.0 100 10 7.3 0.96 43 PECH 18.5 0.20 potassium
cinnamate 41.0 0.22 HMPA 350 4.0 100 5 34.0 0.84 44 PECH 9.25 0.10
Sodium cinnamate 18.7 0.11 HMPA 150 2.0 100 8 17.8 0.87 45 PECH
9.25 0.10 sodium .alpha.-cyano- cinnamate 21.5 0.11 HMPA 150 2.0 60
5 18.3 0.81 46 PECH 9.25 0.10 potassium 21.2 0.11 HMPA 150 2.0 80 6
20.5 0.88 cinnamildeneacetate 47 PECH 9.25 0.10 potassium furfuryl-
acrylate 17.6 0.10 HMPA 150 2.0 70 8 18.1 0.91 48 PECH 9.25 0.10
potassium p-azido- benzoate 20.1 0.10 HMPA 150 2.0 50 7 13.8 0.74
49 PCEVE 5.35 0.05 potassium cinnamate 10.25 0.055 HMPA 50 1.0 80
10 10.6 0.91 50 PCEVE 5.35 0.05 sodium .alpha.-cyano- cinnamate
10.75 0.055 HMPA 50 1.0 50 5 5.2 0.63 51 PCEVE 5.35 0.05 potassium
cinnamildeneacetate 11.2 0.055 HMPA 50 1.0 80 10 11.2 0.90 52 PCEVE
5.35 0.05 potassium furfuryl- acrylate 9.7 0.055 HMPA 50 1.0 80 10
10.1 0.91 53 PCEVE 5.35 0.05 potassium p-azido- benzoate 11.1 0.055
HMPA 50 1.0 70 8 10.3 0.75 54 PVCA 6.03 0.05 potassium cinnamate
10.25 0.055 HMPA 50 1.0 70 5 10.3 0.97 55 PVCA 6.03 0.05 sodium
.alpha.-cyano- cinnamate 10.75 0.055 HMPA 50 0.5 50 5 10.1 0.96 56
PVCA 6.03 0.05 potassium cinnamilideneacetate 11.2 0.055 HMPA 50
1.0 50 5 11.3 0.93 57 PVCA 6.03 0.05 potassium furfuryl- acrylate
9.7 0.055 HMPA 50 1.0 50 5 9.8 0.96 58 PVCA 6.03 0.05 potassium
p-azido- benzoate 11.1 0.055 HMPA 50 -- 50 6 9.3 0.92 Re- fer ence
Ex. PECH 9.25 0.1 potassium cinnamate 20.5 0.11 glyme 150 2.0 60 8
0 --
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Abbreviations of the polymers: PCEA: poly(2-chloroethylacrylate)
PECH: poly(epichlorohydrin) (Except the oligomer in Example 42,
this was used in the form of a rubber like material) PCEVE:
poly(2-chloroethylvinyl ether) PVCA: poly(vinylchloroacetate)
Abbreviations of the solvents: HMPA: hexamethylphosphoroamide
glyme: ethyleneglycoldimethylether
EXAMPLE 59
1.5 g. of the cinnamate ester of the polymers obtained in Example 4
dissolved in 7.5 ml. of cyclohexanone was applied on the surface of
a sheet glass by a whirling applying device. After drying it, a
film of 1 .mu. thickness was obtained on the glass surface.
A step tablet No. 2 (made by Kodak Company) with 21 stepped images
was put on the produced photosensitive film on the surface of the
sheet glass and it was exposed for a period of 21 minutes to a 40
watt chemical lamp at a distance of 10 cm. After the exposure the
unexposed areas of the photosensitive film were dissolved and
washed away with monochlorobenzene. As a result, on the sheet glass
the images were printed, of which those up to the third step were
distinguishable.
EXAMPLE 60
3.0 g. of the cinnamate ester of the polymers obtained in Example
40 and 0.24 g. of 5-nitroacenaphthene as a sensitizer, both
dissolved in 15 ml. of cyclohexanone, were applied on the surface
of a sheet glass by a whirling applying device. After drying them,
a film of less than 1 .mu. thickness was obtained on the surface of
the sheet glass.
A step tablet No. 2 (made by Kodak Company) with 21 stepped images
was then put on the resultant photosensitive film on the glass
surface and it was exposed for a period of 4 minutes to a 40 watt
chemical lamp at a distance of 10 cm. After the exposure the
unexposed areas of the photosensitive film were dissolved and
washed away with monochlorobenzene. As a result, on the sheet glass
the images were printed, of which those up to the 17th step were
distinguishable.
EXAMPLE 61
A copper sheet was coated with 3.0 g. of the cinnamate ester of the
polymer obtained in Exmmple 40 and 0.24 g. of 5-nitroacenaphthene,
both dissolved in 15 ml. of cyclohexanone, to give a film thickness
of 100 .mu., by using a knife-coater. After drying thus provided
coating at 50.degree.C. for 1 hour, a film of 12 .mu. thickness was
obtained on the copper surface.
A negative was then put on the obtained photosensitive film on the
copper surface and it was exposed for a period of 4 minutes to a 40
watt chemical lamp at a distance of 10 cm. After the exposure the
unexposed areas of the film were dissolved and washed away with
monochlorobenzene. Then, this film was treated with an aqueous
solution of ferric chloride for etching, the insoluble areas of the
film were sufficiently resistant to the etching solution, and clear
etching images on the copper were obtained.
It was confirmed that by the observation of the strength of the
film having 12 .mu. thickness on the copper surface by Erichsen
film tester, there were cracks on the copper sheet at D=8.5 mm.,
while the film did not show cracks but showed sufficient resistance
to the applied stress of this value.
EXAMPLE 62
A polyester film was coated with 3.0 g. of the cinnamate ester of
the polymer obtained in Example 40 and 0.24 g. of
5-nitroacenaphthene as a sensitizer, both dissolved in 15 ml. of
cyclohexanone, to give a film thickness of 100 .mu. , by using a
knife-coater. After drying thus formed coating at 50.degree.C. for
1 hour, a film of 12 .mu. thickness was obtained on the polyester
film surface.
The photosensitive film layer on the polyester film surface was
well laminated to the surface of a copper sheet using heated
pressure rollers at a temperature of 100.degree.C. and the
polyester film was easily peeled from the photosensitive film
layer.
A polypropylene film used in place of the polyester one also showed
a successful result.
The above Examples are believed to adequately illustrate all of the
various embodiments of this invention.
* * * * *